Polymers, substrates, methods for making such, and devices comprising the same

ABSTRACT

The present invention relates generally to substrates for making polymers and methods for making polymers. The present invention also relates generally to polymers and devices comprising the same.

RELATED APPLICATIONS

This application claims the benefit of and priority to U.S. ProvisionalApplication Ser. No. 61/761,499, filed Feb. 6, 2013, the disclosure ofwhich is hereby incorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The present invention relates generally to substrates for makingpolymers and methods for making polymers. The present invention alsorelates generally to polymers and devices comprising the same.

BACKGROUND OF THE INVENTION

Conjugated polymeric systems have been an area of research as some canprovide conductive and light emitting and absorbing properties and thushave utility in electronics, molecular electronics and optoeletronics.Conjugated polymers have been made from various monomers and by variousmethods to yield a variety of polymers each with unique physical andelectrical properties. These polymers include poly acetylenes,poly(pyrrole)s, polyanilines, polyazines, poly(p-phenylene vinylene),polycarbazoles, polyindoles, polyazepines poly(thiophene)s,poly(3,4-ethylenedioxythiophene), poly(p-phenylene sulfide),poly(fluorene)s, polyphenylenes, polypyrenes, polyazulenes,polynaphthalenes and polybenzimidazoles. These are generally linearpolymers with variable chain lengths that are described in theliterature.

Polyarylenes are a group of aromatic conjugated polymers that arebranched and dendritic. Polyarylenes are made by the reaction of alkynesor with aromatic halides in the presence of metal catalysts. These aregenerally granular, globular or have a coil morphology. Variations ofthese polymers include polymers made with branched side chains ordendritic structures and polymers with branched monomers incorporatedwith more than one site for polymer extension. These later polymersresult in branched polymers, where the conjugated backbone bifurcates.Each has unique electronic, optical and magnetic properties. However,because all of these reactions are unidirectional, all of the polymerseventually terminate, forming powders or microspheres and do not form anetworked solid material.

The present invention addresses previous shortcomings in the art byproviding substrates for making conjugated polymers and methods formaking conjugated polymers.

SUMMARY OF THE INVENTION

Embodiments according to the invention are directed to substrates,polymers, methods, and devices. In some embodiments, a substrate of thepresent invention may be used to prepare a polymer of the presentinvention. Thus, in some embodiments provided is a substrate asdescribed herein. Pursuant to these embodiments, provided herein is apolymer as described herein.

Also provided herein are methods for preparing a polymer of the presentinvention. One aspect of the present invention comprises a method ofpreparing an organic polymer, comprising polymerizing a multifunctionalsynthetic organic substrate with an oxidase to form said organicpolymer.

An additional aspect of the present invention comprises a method ofpreparing an organic polymer, comprising polymerizing a multifunctionalorganic substrate with an oxidizing agent to form said organic polymer.

A further aspect of the present invention comprises a method ofpreparing a cross-linked polyazine polymer, comprising reacting anorganic substrate comprising at least two aldehydes and/or ketones witha multiamine to form an organic polymer; and oxidizing said organicpolymer to form said cross-linked polyazine polymer.

In a further aspect of the present invention, provided is a device, suchas, but not limited to, an electrochemical device, comprising a polymerof the present invention.

The foregoing and other aspects of the present invention will now bedescribed in more detail with respect to other embodiments describedherein. It should be appreciated that the invention can be embodied indifferent forms and should not be construed as limited to theembodiments set forth herein. Rather, these embodiments are provided sothat this disclosure will be thorough and complete, and will fullyconvey the scope of the invention to those skilled in the art.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-D show polymer sheet networks prepared using′compound 2 andeither 5-hydroxyindole, serotonin, or indole. A) Compound 2 and5-hydroxyindole networked polymer at 200× magnification. B) Compound 2and serotonin networked polymer at 200× magnification. C) Compound 2 andindole networked polymer at 200× magnification. D) Compound 2 and indolenetworked polymer at 400× magnification.

FIG. 2 shows the synthesis of the following azadiene polymers (from topto bottom): 2,5-furan azadiene polymer, benzene-1,3-azadiene polymer,benzene-1,4-azadiene polymer, 4,4-biphenyl azadiene polymer,2,3-naphthalene azadiene polymer, 2,5-thiophene azadiene polymer,3,4-dimethyl-2,5-pyrrole azadiene polymer, and benzene-1,4-methylazadiene polymer.

FIG. 3 shows the synthesis of a networked benzene-1,3,5-azadiene polymerusing 1,3,5 benzene tricarboxaldehyde and hydrazine.

FIG. 4 shows a cyclic voltammetery of 3,4 dimethyl pyrrole azadienelinear conjugated polymer.

FIG. 5 shows the indole capped 2,5 azadiene polymer polymer (bottom) andthe final networked indole capped polymer after oxidation (top).

FIGS. 6A-C show A) the synthesis of an indole cappedbenzene-1,3,5-azadiene network polymer; B) shows this polymer prior tooxidation (left) and after oxidation (right) with ammonium persulfate toproduce an indole crosslinked benzene 1,3,5-azadiene network polymer; C)shows an absorption spectrum for the oxidized cross-linked indole capped1,3,5 benzene azadiene polymer; and D) shows a cyclic voltammetery ofthe polymer.

FIG. 7 shows the synthesis of the following multifunctional substrates(from top to bottom): 2-indole azadiene, thianaphthene-2-azadiene,5-indole azadiene, and 2-pyrrole azadiene.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be described more fully hereinafter. Thisinvention may, however, be embodied in different forms and should not beconstrued as limited to the embodiments set forth herein. Rather, theseembodiments are provided so that this disclosure will be thorough andcomplete, and will fully convey the scope of the invention to thoseskilled in the art.

The terminology used in the description of the invention herein is forthe purpose of describing particular embodiments only and is notintended to be limiting of the invention. As used in the description ofthe invention and the appended claims, the singular forms “a”, “an” and“the” are intended to include the plural forms as well, unless thecontext clearly indicates otherwise.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this invention belongs. It will befurther understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the present applicationand relevant art and should not be interpreted in an idealized or overlyformal sense unless expressly so defined herein. The terminology used inthe description of the invention herein is for the purpose of describingparticular embodiments only and is not intended to be limiting of theinvention. All publications, patent applications, patents and otherreferences mentioned herein are incorporated by reference in theirentirety for the teachings relevant to the sentence and/or paragraph inwhich the reference is presented. In case of a conflict in terminology,the present specification is controlling.

Also as used herein, “and/or” refers to and encompasses any and allpossible combinations of one or more of the associated listed items, aswell as the lack of combinations when interpreted in the alternative(“or”).

Unless the context indicates otherwise, it is specifically intended thatthe various features of the invention described herein can be used inany combination. Moreover, the present invention also contemplates thatin some embodiments of the invention, any feature or combination offeatures set forth herein can be excluded or omitted. To illustrate, ifthe specification states that a complex comprises components A, B and C,it is specifically intended that any of A, B or C, or a combinationthereof, can be omitted and disclaimed.

As used herein, the transitional phrase “consisting essentially of” (andgrammatical variants) is to be interpreted as encompassing the recitedmaterials or steps “and those that do not materially affect the basicand novel characteristic(s)” of the claimed invention. See, In re Herz,537 F.2d 549, 551-52, 190 U.S.P.Q. 461, 463 (CCPA 1976) (emphasis in theoriginal); see also MPEP §2111.03. Thus, the term “consistingessentially of” as used herein should not be interpreted as equivalentto “comprising.”

The term “about,” as used herein when referring to a measurable valuesuch as an amount or concentration and the like, is meant to encompassvariations oft 20%, ±10%, 5%, ±1%, ±0.5%, or even ±0.1% of the specifiedamount. A range provided herein for a measureable value may include anyother range and/or individual value therein.

It will be understood that when an element or layer is referred to asbeing “on,” “connected to,” or “coupled with” another element or layer,it can be directly on, connected, or coupled with the other element orlayer or intervening elements or layers may be present. In contrast,when an element is referred to as being “directly on,” “directlyconnected to,” or “directly coupled with” another element or layer,there are no intervening elements or layers present.

“Moiety” or “moieties,” as used herein, refer to a portion of amolecule, such as a portion of a substrate, typically having aparticular functional or structural feature. For example, a moiety maycomprise a linking group (a portion of a molecule connecting at leasttwo other portions of the molecule). In some embodiments, a moiety maybe a reactive portion of a substrate.

“Substituted” as used herein to describe a chemical structure, group, ormoiety, refers to the structure, group, or moiety comprising one or moresubstituents. As used herein, in cases in which a first group is“substituted with” a second group, the second group is attached to thefirst group whereby a moiety of the first group (typically a hydrogen)is replaced by the second group. The substituted group may contain oneor more substituents that may be the same or different.

“Substituent” as used herein references a group that replaces anothergroup in a chemical structure. Typical substituents include nonhydrogenatoms (e.g., halogens), functional groups (such as, but not limited to,amino, sulfhydryl, carbonyl, hydroxyl, alkoxy, carboxyl, silyl,silyloxy, phosphate and the like), hydrocarbyl groups, and hydrocarbylgroups substituted with one or more heteroatoms. Exemplary substituentsinclude, but are not limited to, alkyl, lower alkyl, halo, haloalkyl,alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, heterocyclo,heterocycloalkyl, aryl, arylalkyl, lower alkoxy, thioalkyl, hydroxyl,thio, mercapto, amino, imino, halo, cyano, nitro, nitroso, azido,carboxy, sulfide, sulfone, sulfoxy, phosphoryl, silyl, silylalkyl,silyloxy, boronyl, and modified lower alkyl.

“Alkyl” as used herein alone or as part of another group, refers to alinear (“straight chain”), branched chain, and/or cyclic hydrocarboncontaining from 1 to 30 or more carbon atoms. In some embodiments, thealkyl group may contain 1, 2, or 3 up to 4, 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or30 carbon atoms. Representative examples of alkyl include, but are notlimited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl,iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl,3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl,n-octyl, n-nonyl, n-decyl, and the like. “Lower alkyl” as used herein,is a subset of alkyl and refers to a straight or branched chainhydrocarbon group containing from 1 to 4 carbon atoms. Representativeexamples of lower alkyl include, but are not limited to, methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, and the like. Theterm “alkyl” or “loweralkyl” is intended to include both substituted andunsubstituted alkyl or loweralkyl unless otherwise indicated and thesegroups may be substituted with groups such as, but not limited to,polyalkylene oxides (such as PEG), halo (e.g., haloalkyl), alkyl,haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl,arylalkyl, heterocyclo, heterocycloalkyl, hydroxyl, alkoxy (therebycreating a polyalkoxy such as polyethylene glycol), alkenyloxy,alkynyloxy, haloalkoxy, cycloalkoxy, cycloalkylalkyloxy, aryloxy,arylalkyloxy, heterocyclooxy, heterocyclolalkyloxy, mercapto,alkyl-S(O)_(m), haloalkyl-S(O)_(m), alkenyl-S(O)_(m),cycloalkyl-S(O)_(m), cycloalkylalkyl-S(O)_(m), aryl-S(O)_(m),arylalkyl-S(O)_(m), heterocyclo-S(O)_(m), heterocycloalkyl-S(O)_(m),amino, carboxy, alkylamino, alkenylamino, alkynylamino, haloalkylamino,cycloalkylamino, cycloalkylalkylamino, arylamino, arylalkylamino,heterocycloamino, heterocycloalkylamino, disubstituted-amino, acylamino,acyloxy, ester, amide, sulfonamide, urea, alkoxyacylamino, aminoacyloxy,nitro or cyano, where m=0, 1, 2 or 3.

“Alkenyl” as used herein alone or as part of another group, refers tolinear (“straight chain”), branched chain, and/or cyclic containing from1 to 30 or more carbon atoms (or in loweralkenyl 1 to 4 carbon atoms)which include 1 to 10 or more double bonds in the hydrocarbon chain. Insome embodiments, the alkenyl group may contain 1, 2, 3, 4, 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26,27, 28, 29, or 30 carbon atoms. Representative examples of alkenylinclude, but are not limited to, methylene (═CH₂), vinyl (—CH═CH₂),allyl (—CH₂CH═CH₂), 2-butenyl, 3-butenyl, 4-pentenyl, 3-pentenyl,2-hexenyl, 3-hexenyl, 2,4-heptadiene, and the like. The term “alkenyl”or “loweralkenyl” is intended to include both substituted andunsubstituted alkenyl or loweralkenyl unless otherwise indicated andthese groups may be substituted with groups such as those described inconnection with alkyl and loweralkyl above.

“Conjugated,” as used herein, refers to a moiety or compound comprisingat least two double bonds. In some embodiments, a substrate of thepresent invention may be conjugated. In certain embodiments, aconjugated moiety or compound may be aromatic. The term “aryl” is usedherein to refer to an aromatic moiety or compound. “Aryl” may be asingle aromatic ring or multiple aromatic rings that are fused together,linked covalently, or linked to a common group, such as, but not limitedto, a methylene or ethylene moiety. The common linking group also may bea carbonyl, as in benzophenone, or oxygen, as in diphenylether, ornitrogen, as in diphenylamine. The term “aryl” specifically encompassesheterocyclic aromatic compounds. The aromatic ring(s) may comprisephenyl, naphthyl, tetrahydronaphthyl, biphenyl, azulenyl, indanyl,indenyl, diphenylether, diphenylamine and benzophenone, among others. Inparticular embodiments, the term “aryl” means a cyclic aromaticcomprising about 5 to about 50 or more carbon atoms, and includes 5- and6-membered hydrocarbon and heterocyclic aromatic rings. In someembodiments, a substrate of the present invention is aromatic.

“Multiamine,” as used herein, refers to a compound comprising two ormore amines. A multiamine may comprise 2, 3, 4, 5, 6, 7, or more amines.In some embodiments, a multiamine comprises 2 amines and thus is adiamine. Exemplary multiamines include, but are not limited to,hydrazine, triaminobenzene, ethylenediamine, and any combinationthereof.

“Monocarbonyl compound,” as used herein, refers to a compound comprisingonly one carbonyl group. A monocarbonyl compound can comprise analdehyde (i.e., a monoaldehyde) or a ketone (i.e., a monoketone). Insome embodiments, a monocarbonyl compound has the following structure

wherein

R is a conjugated or aromatic moiety; and

R¹ is selected from the group consisting of hydrogen, alkyl, and analkylene.

According to some embodiments of the present invention, provided hereinare substrates that may be used to prepare a conjugated polymer.“Substrate,” as used herein, refers to a compound that can bepolymerized to form a polymer. A substrate may be polymerized usingchemical oxidative polymerization and/or enzymatic oxidativepolymerization. In some embodiments, a substrate may be acted on by anenzyme. For example, a substrate may be oxidized by an enzyme. In otherembodiments, a substrate may not be acted on by an enzyme. In someembodiments, a substrate may be polymerized using an oxidizing agent. Asubstrate may be a synthetic substrate or a natural substrate, either ofwhich may be polymerized using chemical oxidative polymerization and/orenzymatic oxidative polymerization.

“Synthetic,” as used herein in reference to a substrate, refers to asubstrate that is not a natural substrate of an oxidase. Thus, asynthetic substrate is not found in nature as a substrate for an oxidaseand thus is an unnatural substrate. In some embodiments, a syntheticsubstrate may be synthetically prepared, and optionally one or morecompounds may be obtained or derived from nature and used tosynthetically prepare a synthetic substrate.

“Natural,” as used herein in reference to a substrate, refers to asubstrate that is a natural substrate of an oxidase. Thus, a naturalsubstrate is found in nature as a substrate for an oxidase. In someembodiments, a natural substrate may be synthetically prepared, andoptionally one or more compounds may be obtained or derived from natureand used to synthetically prepare a natural substrate.

“Organic,” as used herein, refers to a compound, substrate, and/orpolymer comprising carbon. In some embodiments, an organic substrate maycomprise a metal, such as, but not limited to copper, gold, aluminum,lithium, calcium, sodium, tungsten, zinc, iron, platinum, tin, lead,titanium, potassium, silver, rubidium, and any combination thereof. Incertain embodiments, an organic substrate is exposed, contacted, and/ordoped with a metal and/or metal containing compound such that the metalbecomes incorporated with the substrate and/or forms a complex with thesubstrate.

In certain embodiments, a substrate of the present invention ismultifunctional. “Multifunctional,” as used herein in reference to asubstrate, refers to an organic substrate that comprises at least twomoieties that are configured to provide polymerization in more than onedirection. A multifunctional organic substrate may comprise 2, 3, 4, 5,or more moieties that may be the same and/or different. In someembodiments, a multifunctional substrate may be a synthetic substrate.In other embodiments, a multifunctional substrate may be a naturalsubstrate. Exemplary multifunctional organic substrates include, but arenot limited to, those shown in Scheme 1.

In some embodiments, a multifunctional organic substrate comprises atleast two reactive moieties. In certain embodiments, a multifunctionalorganic substrate comprises at least three reactive moieties. “Reactivemoiety” and “reactive moieties,” as used herein, refer to moieties thatcan be oxidized by an oxidase and/or an oxidizing agent. Exemplaryreactive moieties include, but are not limited to, an indole, a pyrrole,a catechol, a tyrosyl, a catecholamine, and any combination thereof. Incertain embodiments, a substrate comprises one or more reactive moietiesselected from the group consisting of a 6-hydroxyindole, a5-hydroxyindole, a 5,6-dihydroxyindole, and any combination thereof.

In certain embodiments, a reactive moiety may comprise a conjugatedmoiety. A substrate of the present invention may comprise one or more,such as 2, 3, 4, or more, reactive moieties each of which may comprise aconjugated moiety. In some embodiments, a reactive moiety may comprisean aromatic moiety. A substrate of the present invention may compriseone or more, such as 2, 3, 4, or more, reactive moieties each of whichmay comprise an aromatic moiety.

As those skilled in the art will recognize, a polymerization reactionmay occur or involve one or more reactive sites within a moiety. Thus, areactive moiety may have at least 2, 3, 4, 5, 6, 7, 8, 9, 10, or morereactive sites. For example, as shown in Scheme 2, for5,6-dihydroxyindole, polymerization may occur or take place at the C2,C3, C4, and/or C7 position, and a bond may be created between at leastone of these reactive sites and at least one reactive site of anotherreactive moiety.

A reactive site within a moiety of a substrate of the present inventionmay be modified and/or blocked with a substituent, such as, but notlimited to an alkyl. This may cause a polymerization reaction to occuror involve one or more different reactive sites within a reactive moietyof a substrate.

A substrate of the present invention may comprise two or more reactivemoieties that may be joined by a linker. “Linker” as used herein refersto a moiety that serves as a point of attachment for two or morereactive moieties that may be same and/or different. Two or morereactive moieties may be bound covalently to a linker or may be fused toa linker. A linker may be a conjugated moiety, and in some embodiments alinker may be an aromatic moiety. In certain embodiments, a method ofthe present invention may result in a linker becoming conjugated. Forexample, polymerization of a substrate using either an oxidase or anoxidizing agent may result in a conjugated linker.

In some embodiments, a substrate of the present invention is monomeric.“Monomeric,” as used herein in reference to a substrate, refers to asubstrate that has not been linked or bound to another substrate. Thus,the substrate is not oligomeric or polymeric. While a substrate may haveone or more of the same moieties within the substrate, a monomericsubstrate does not comprise two or more substrates that have been linkedtogether. For example, the substrates provided in Scheme 1 are monomericas they have not been linked to another substrate.

In some embodiments, a substrate of the present invention comprises asubstrate as described herein. In certain embodiments, a substrate ofthe present invention comprises a substrate provided in Scheme 1 and/ora substrate described in the examples provided herein. A substrate ofthe present invention may be used to prepare a polymer of the presentinvention. In some embodiments, a polymer of the present inventioncomprises a polymer as described herein. In certain embodiments, apolymer of the present invention comprises a polymer described in theexamples provided herein, such as, but not limited to, a polymerprovided in Table 2. A method of the present invention may be used toprepare a polymer of the present invention. In some embodiments, asubstrate of the present invention may be used in a method of thepresent invention to prepare a polymer of the present invention.

According to some embodiments of the present invention, a method ofpreparing an organic polymer is provided, the method comprisingpolymerizing a multifunctional synthetic organic substrate with anoxidase to form the organic polymer. “Oxidase,” as used herein, refersto an enzyme that oxidizes a substrate. Exemplary oxidases include, butare not limited to, phenol oxidase, a polyphenol oxidase, a catecholoxidase, a tyrosinase, a laccase, monophenol monooxygenase, phenolase,monophenol oxidase, cresolase, monophenolase, tyrosine-dopa oxidase,monophenol monooxidase, monophenol dihydroxyphenylalanine:oxygenoxidoreductase, N-acetyl-6-hydroxytryptophan oxidase,dihydroxy-L-phenylalanine oxygen oxidoreductase, o-diphenol:O₂oxidoreductase, catecholase, o-diphenol oxidase, monophenol oxidase,cresolase, and any combination thereof.

In some embodiments, a method of the present invention may comprisepolymerizing a multifunctional synthetic organic substrate comprising atleast two reactive moieties with an oxidase to form an organic polymer.In certain embodiments, a method of the present invention may comprisepolymerizing a multifunctional synthetic organic substrate comprising atleast three reactive moieties with an oxidase to form an organicpolymer. When a multifunctional synthetic organic substrate comprises atleast two reactive moieties, a networked organic polymer may be formed.“Networked,” as used herein in reference to a polymer of the presentinvention, refers to a cross-linked polymer (i.e., a polymer comprisingone or more polymer chains that are linked together either directlythrough covalent attachment and/or through a moiety or group), whereinthe polymer chains are interconnected at two or more locations withinthe polymer chains. In some embodiments, the cross-links (i.e., thelinkages connecting the one or more polymer chains) in a networkedpolymer of the present invention comprise a conjugated moiety.

A method of the present invention may comprise co-polymerizing amultifunctional synthetic organic substrate with an additional substrateusing an oxidase to form an organic polymer. The additional substratemay be any organic compound. In some embodiments, an additionalsubstrate may comprise a natural substrate of an oxidase. In someembodiments, an additional substrate may comprise multifunctionalorganic substrate, such as, but not limited to, a differentmultifunctional synthetic organic substrate. Thus, the formed organicpolymer may comprise one or more different units.

Prior to or concurrently with the polymerizing step, a metal may beadded to the substrate and/or reaction mixture. Thus, a substrate and/ororganic polymer may be doped with a metal, ionic liquid, ionomer, and/orother dopant(s). In some embodiments, a dopant may oxidize or reduce theconjugated polymer. In some embodiments, doping a substrate and/ororganic polymer may increase the electrical properties of the organicpolymer.

In certain embodiments, after the polymerizing step, the organic polymermay be reacted with an oxidizing agent. This may provide furthercross-linking in the organic polymer. Exemplary oxidizing agentsinclude, but are not limited to, ammonium persulfate, iron (III)chloride, hydrogen peroxide, urea peroxide, melamine peroxide, sodiumperborate, potassium perborate, sodium percarbonate, potassiumpercarbonate, potassium persulfate, sodium persulfate, ferric nitrate,diammonium cerium nitrate, iron sulfate, ozone, potassium periodate, andany combination thereof. In some embodiments, an organic substrate maybe co-reacted with the organic polymer and oxidizing agent. The organicsubstrate according to some embodiments may comprise a multifunctionalorganic substrate.

According to further embodiments of the present invention, provided is amethod of preparing an organic polymer, the method comprisingpolymerizing a multifunctional organic substrate with an oxidizing agentto form said organic polymer. Exemplary oxidizing agents for us in themethod include, but are not limited to, those described herein. In someembodiments, a method of the present invention may comprise polymerizinga multifunctional organic substrate comprising at least two reactivemoieties with an oxidase to form an organic polymer. In certainembodiments, a method of the present invention may comprise polymerizinga multifunctional organic substrate comprising at least three reactivemoieties with an oxidase to form an organic polymer. When amultifunctional organic substrate comprises at least two reactivemoieties, a networked organic polymer may be formed.

A method of the present invention may comprise co-polymerizing amultifunctional organic substrate with an additional substrate using anoxidizing agent to form an organic polymer. The additional substrate maybe any organic compound. In some embodiments, an additional substratemay comprise a natural substrate of an oxidase. In some embodiments, anadditional substrate may comprise a different multifunctional organicsubstrate. Thus, the formed organic polymer may comprise one or moredifferent units.

Prior to or concurrently with the polymerizing step, a metal may beadded to the substrate and/or reaction mixture. Thus, a substrate and/ororganic polymer may be doped with a metal, ionic liquid, ionomer, and/orother dopant(s). In some embodiments, a dopant may oxidize or reduce theconjugated polymer. In some embodiments, doping a substrate and/ororganic polymer may increase the electrical properties of the organicpolymer.

In certain embodiments, after the polymerizing step, the organic polymermay be reacted a second time with an oxidizing agent. This may providefurther cross-linking in the organic polymer. In some embodiments, anorganic substrate may be co-reacted with the organic polymer andoxidizing agent. The organic substrate according to some embodiments maycomprise a multifunctional organic substrate.

In some embodiments, a method of the present invention may comprisepolymerizing a synthetic organic substrate comprising an aldehyde, suchas, but not limited to, at least two or three aldehydes, with an oxidaseto form an organic polymer, then reacting the organic polymer with amultiamine to cross-link the organic polymer. As those skilled in theart will recognize, an organic polymer may already comprise cross-linksand thus the reacting step may comprise providing further or additionalcross-links within the organic polymer. In certain embodiments, anetworked polymer may be formed.

In some embodiments, a method of the present invention may comprisepolymerizing a synthetic organic substrate comprising a ketone, such as,but not limited to, at least two or three ketones, with an oxidaseand/or oxidizing agent to form an organic polymer, then reacting theorganic polymer with a multiamine to cross-link the organic polymer. Asthose skilled in the art will recognize, an organic polymer may alreadycomprise cross-links and thus the reacting step may comprise providingfurther or additional cross-links within the organic polymer. In certainembodiments, a networked polymer may be formed.

According to an additional embodiment of the present invention, providedis a method of preparing a cross-linked polyazine polymer comprisingreacting an organic substrate comprising at least two aldehydes and/orketones with a multiamine to form an organic polymer, and oxidizing saidorganic polymer to form said cross-linked polyazine polymer. Theoxidizing step may be carried out by enzymatic oxidative polymerizationwith an oxidase and/or by chemical oxidative polymerization with anoxidizing agent. The organic substrate may be a natural or syntheticsubstrate.

An organic substrate comprising at least two aldehydes and/or ketonesmay comprise a conjugated moiety. In some embodiments, an organicsubstrate comprising at least two aldehydes and/or ketones may comprisean aromatic moiety. Optionally, the at least two aldehydes and/orketones may be attached and/or bound to the aromatic moiety. In someembodiments, an organic substrate has the structure

wherein

R is a conjugated or aromatic moiety; and

R¹ and R² are each independently selected from the group consisting ofhydrogen, alkyl, and alkenyl, and the organic polymer has a structurecomprising (RCNNC)_(n)RC(O)R¹, (RCNNC)_(n)RC(O)R², or (RCNNC)_(n)CNN,wherein n is a number from 2 to 1,000,000.

An organic substrate according to some embodiments may comprise at leastthree aldehydes and/or ketones, and may in some embodiments react with amultiamine to form a networked organic polymer. In some embodiments, anorganic substrate has the structure

wherein

R is a conjugated or aromatic moiety; and

R¹, R², and R³ are each independently selected from the group consistingof hydrogen, alkyl, and alkenyl, and wherein the organic polymer has astructure comprising (RC₃N₃N₃C₃)_(n)RC(O)R¹, (RC₃N₃N₃C₃)_(n)RC(O)R²,RC₃N₃N₃C₃)_(n)RC(O)R³, or (RC₃N₃N₃C₃)_(n)CNN, wherein n is a number from2 to 1,000,000.

In certain embodiments, an organic substrate may comprise an indole, apyrrole, a phenol, a thiophene, a furan, a thianaphthene, an acetylene,a catechol, a tyrosyl, a catecholamine, and any combination thereof. Insome embodiments, an organic substrate comprises an indole or a pyrrolethat may be substituted with at least two aldehydes and/or ketones.

Prior to the oxidizing step, a method of preparing a cross-linkedpolyazine polymer may comprise reacting the organic polymer with asecond organic substrate comprising at least two aldehydes and/orketones and a multiamine. In some embodiments, the second organicsubstrate is different than the first organic substrate and thus aheteropolymer is formed. “Heteropolymer” as used herein refers to anorganic polymer comprising two or more different polymeric units.

Prior to or concurrently with one or more steps in a method of preparinga cross-linked polyazine polymer, a metal may be added to the substrateand/or reaction mixture. Thus, a substrate, organic polymer, and/orcross-linked polyazine polymer may be doped with a metal, ionic liquid,ionomer, and/or the like. In some embodiments, doping a substrate,organic polymer, and/or cross-linked polyazine polymer with a metal mayincrease the electrical properties of the organic polymer. In certainembodiments, the oxidizing step is carried out with a reagent, such as,but not limited to, iron (III) chloride, that may oxidize the organicpolymer and dope the organic polymer and/or cross-linked polyazinepolymer with a metal.

In some embodiments, a method of preparing a cross-linked polyazinepolymer may comprise reacting a monocarbonyl compound with the organicpolymer and a multiamine prior to the oxidizing step. Reaction of theorganic polymer with a multiamine and monocarbonyl compound can resultin a capped organic polymer, meaning that the monocarbonyl compound maybe added onto the end of one or more of the polymer chains. In someembodiments, a monocarbonyl compound has the structure

wherein

R is a conjugated or aromatic moiety; and

R¹ is selected from the group consisting of hydrogen, alkyl, andalkenyl.

A substrate of the present invention and/or a method of the presentinvention may provide a conjugated organic polymer and/or a cross-linkedpolyazine polymer.

According to further embodiments of the present invention, provided isan electrochemical device comprising an organic polymer and/or across-linked polyazine polymer of the present invention. Anelectrochemical device according to embodiments of the invention maycomprise a working electrode, a counter electrode, and an organicpolymer and/or cross-linked polyazine polymer of the present invention,wherein said working electrode is in operative communication with saidcounter electrode, and the organic polymer and/or cross-linked polyazinepolymer is in operative communication with said working electrode orsaid counter electrode. In certain embodiments, the organic polymerand/or a cross-linked polyazine polymer may be conjugated, and mayoptionally comprise a metal.

In some embodiments, an organic polymer and/or cross-linked polyazinepolymer of the present invention is disposed on at least a portion of aworking electrode. The organic polymer and/or cross-linked polyazinepolymer may be directly or indirectly in contact with at least a portionof a working electrode. In certain embodiments, an organic polymerand/or cross-linked polyazine polymer of the present invention may beinterposed between a working electrode and a counter electrode. In someembodiments, an electrochemical device comprises an organic polymerand/or cross-linked polyazine polymer of the present invention that maybe in the form of a coating in contact with or on a working electrodeand/or a counter electrode.

An electrochemical device of the present invention encompasses all typesof devices to perform electrochemical reactions. Exemplaryelectrochemical device include, but are not limited to, a battery, afuel cell, a solar cell, a capacitor or a device formed of a combinationthereof, a supercapacitor, an ultracapacitor, an electric double-layercapacitor, and any combination thereof.

The present invention is explained in greater detail in the followingnon-limiting Examples.

EXAMPLES Example 1

All reactions were carried out in approximately 50 mM potassiumphosphate buffer, pH 6.5 with approximately 5 mM substrate and mushroomtyrosinase (polyphenol oxidase) Sigma T3824 in an amount of 100 to10,000 units. Reaction volumes varied from 200 μl to 2 ml. In caseswhere substrates were not completely solubilized, then a saturatedsolution was used as the limit of solubility. In some cases, a solutionof DMSO was used to increase solubility of the substrates. The enzymewas tested and shown to retain activity up to 50% DMSO. These cases areindicated in Table 1. The reactions were observed over a 24 hour periodfor the production of polymers, and the presence and color of polymerand solution was recorded.

The production of polymers in each reaction was visible as a precipitatein the well of a 96 well plate or in the reaction mixture on a glassslide.

TABLE 1 Testing of polymer production in enzymatic tyrosinase(polyphenyl oxidase) reaction. Result Notes Substrate Tested Tyrosine*++ Black powdery polymer precipitate N-methyl tyrosine ++ Black powderypolymer precipitate, N can be blocked. Tyramine* +++ Black stickypolymer precipitate. Forms faster than tyrosine. Some iridescence infilms formed at surface. Tyramine HCl* +++ Black brown sticky polymerprecipitate. Forms faster than tyrosine. Some iridescence.5-hydroxyindole* +++ Black polymer precipitate. 6 Hydroxyindole ++ Blackpolymer precipitate. 2 Hydroxy carbazole** − Darker brown than controlbut no clear polymer. May be quinone. Harmalol HCl dehydrate** − Noreaction. Indole − No reaction. Beta phenylethylamine HCL +/− Some whiteprecipitate, may be polymer or compound coming out of solution.Crosslinking Substrates Tested 1,3,5 Tris(4hydroxyphenyl)benzene +Cloudy precipitate with a slight brown/orange (20% DMSO) color insolution. Color may indicate the quinone. 2,6 dihydroxnaphthalene + Someprecipitate, may be polymer or compound coming out of solution. After 24hours there was some dark color to the polymer indicating some polymerformed. Mixtures tested Tyrosine + Tyramine +++ Black polymerprecipitate. Tyrosine + 2-Hydroxy carbazole** +++ Black polymerprecipitate. Tyrosine + Harmalol HCl** +++ Reacts faster than Tryosinealone, harmalol may be incorporated as a reactant. Tyrosine + 1,3,5-Tris(4- +++ Black polymer precipitate. hydroxyphenyl) benzene** Tyramine +2-Hydroxy carbazole** +++ Black polymer precipitate. Tyramine + HarmalolHCl** +++ Reacts faster than Tryosine alone, harmalol may beincorporated as a reactant. Tyramine + 1,3,5-Tris (4- +++ Black polymerprecipitate. hydroxyphenyl) benzene** 2-Hydroxy carbazole** + Harmalol +Fine dark precipitate HCl** 2-Hydroxy carbazole** + 1,3,5-Tris −(4-hydroxyphenyl) benzene** Harmalol HCl + 1,3,5-Tris (4- −hydroxyphenyl) benzene** *Reported substrate for phenol oxidases. **Dissolved in 20% DMSO. +++ Reacted within about 1 hour; ++ reactedwithin about 3 hours; + reacted within about 24 hours; +/− inconclusiveresults; − no reaction.

Example 2 Creation of Networked Polymer Sheets with Compound 2

In 50 μl of DMSO, 10 mg of compound 2 (Scheme 3) was dissolved and addedto 10 mg of either indole, 5-hydroxyindole, 6-hydroxyindole, orserotonin that was dissolved in 50 μl DMSO.

The samples were polymerized by oxidation with 100 μl of 0.8 M ammoniumpersulfate in water in the case of indole and 5-hydroxyindole and 100 μlof 0.2 M ammonium persulfate in water in the case of 6-hydroxyindole andserotonin. These were compared to solutions of 50 μl 5-hydroxyindole,6-hydroxyindole, and serotonin polymerized with equal volumes of thesame concentrations of ammonium persulfate without compound 2. Sheets ofnetworked polymer were produced and examined microscopically at 200× and400× magnification as shown in FIGS. 1A-D. 6-hydroxyindole did notnetwork into a polymer sheet under these conditions. Controls of indole,5-hydroxyindole and 6-hydroxyindole alone only formed amorphous darkparticulate precipitates.

Example 3

Polyazine polymers were synthesized as follows. 0.2 g of variousdicarboxaldehydes were reacted with 0.03 g of hydrazine monohydrate(65%) or triaminobenzene in 15 ml of ethanol or acetonitrile to yieldazadiene polymers (Table 2). In some cases, as with ketones, the PH wasadjusted to about 5.0. In some cases these polymers were furthermodified (i.e., capped) by addition of indole or pyrrole moieties on theends of the polymer chain by reacting the washed azadiene polymer withan 0.1 g of indole aldehydes or pyrrole aldehydes and 0.015 g ofhydrazine monohydrate (15%) in 5 ml of ethanol or acetonitrile asdescribed in Table 2. These resulted in capped polymers with the endscapped with one or more indole or pyrrole groups. Some of the cappedpolymers were subsequently crosslinked with an excess of 0.8 M ammoniumpersulfate.

FIG. 2 shows the synthesis of the azadiene polymers. FIG. 3 shows thesynthesis of a networked benzene-1,3,5-azadiene polymer using 1,3,5benzene tricarboxaldehyde and hydrazine. FIG. 4 shows a cyclicvoltammetery of 3,4 dimethyl pyrrole azadiene linear conjugated polymer.

TABLE 2 Synthetic details for preparing polyazine polymers. Cross-Capping Capping linking Reactant 1 Reactant 2 Solvent Product Reactant 1reactant 2 Solvent Product reactant 2,5-furan Hydrazine Ethanol2,5-furan azadiene dicarboxaldehyde polymer 2,5-furan Hydrazine Ethanol2,5-furan azadiene Indole-5- Hydrazine acetonitrile Indole cappedAmmonium dicarboxaldehyde polymer carboxaldehyde furan-2,5,- persulfateazadiene polymer 2,5-furan Hydrazine Ethanol 2,5-furan azadiene Pyrrole-Hydrazine acetonitrile Pyrrole capped Ammonium dicarboxaldehyde polymer2carboxaldehyde furan-2,5,- persulfate azadiene polymer Benzene-1,3-Hydrazine Ethanol Benzene-1,3- dicarboxaldehyde azadiene polymerBenezene-1,4- Hydrazine Ethanol Benzene-1,4- dicarboxaldehyde azadienepolymer 4,4-biphenyl Hydrazine Ethanol, 4,4-biphenyl dicarboxaldehydeacetonitrile azadiene polymer 2,3-naphthalene Hydrazine Ethanol,2,3-naphthalene dicarboxaldehyde acetonitrile azadiene polymer2,5-thiophene Hydrazine Ethanol 2,5-thiophene dicarboxaldehyde azadienepolymer 3,4-dimethyl-2,5- Hydrazine Ethanol 3,4-dimethyl-2,5- pyrrolepyrrole azadiene dicarboxaldehyde polymer Benzene-1,3,5- HydrazineEthanol, Benzene-1,3,5- tricarboxaldehyde acetonitrile azadiene networkpolymer Benzene-1,3,5- Hydrazine Ethanol, Benzene-1,3,5- 5-carboxyindoleHydrazine acetonitrile Indole capped tricarboxaldehyde acetonitrileazadiene network Benzene-1,3,5- polymer azadiene network polymerBenzene-1,3,5- Hydrazine Ethanol, Benzene-1,3,5- 5-carboxyindoleHydrazine acetonitrile Indole capped Ammonium tricarboxaldehydeacetonitrile azadiene network Benzene-1,3,5- persulfate polymer azadienenetwork polymer Benzene-1,3,5- Hydrazine Ethanol, Benzene-1,3,5-5-carboxyindole Hydrazine acetonitrile Indole capped Irontricarboxaldehyde acetonitrile azadiene network Benzene-1,3,5- Chloridepolymer azadiene (FeCl₃) network polymer Benzene-1,3,5- TriaminobenzeneEthanol, Benzene-imine tricarboxaldehyde acetonitrile network polymer1,4-diacetyl Hydrazine Ethanol Benzene-1,4- benzene methyl azadienepolymer 1,3,5-triacetyl Hydrazine Ethanol, Benezene-1,3,5- benzeneacetonitrile methyl azadiene network polymer

Example 4

A polyazine polymer of furan 2,5-azadiene was synthesized as follows.0.2 g of furan 2,5-dicarboxaldehyde was reacted with 30 μl of hydrazinemonohydrate (65%) in 15 ml of ethanol to yield the furan 2,5-azadienepolymer (Scheme 4).

This polymer was further modified by the addition of indole or pyrrolemoieties on the ends of the polymer chain by reacting the ethanol washedpolymer (0.05 g) with 0.05 g of indole-5-carboxaldehyde or 0.05 g ofpyrrole-2-carboxaldehyde and 12 μl of hydrazine monohydrate (65%) in 5ml of acetonitrile to yield indole or pyrrole capped polymersrespectively. These polymers were subsequently crosslinked intonetworked lattices by reacting with an excess of 0.8 M ammoniumpersulfate. FIG. 5 shows the indole capped 2,5 azadiene polymer polymer(bottom) and the final networked indole capped polymer after oxidation(top).

Example 5

An indole capped 1,3,5 benzene azadiene networked polymer was prepared.0.25 g of 1,3,5 tricarbox-aldehyde was reacted with 100 μl of hydrazinemonohydrate (65%) in 10 ml of acetonitrile. To this mixture 1 g of5-carboxyindol was added to terminate the polymerization reaction whilecapping the polymer chain extensions. FIG. 6A shows the synthesis of anindole capped benzene-1,3,5-azadiene network polymer, which wassubsequently reacted with either ammonium persulfate or FeCl3 oxidizingagents to crosslink the indoles, thereby producing an indole crosslinkedbenzene 1,3,5-azadiene network polymer. The polymer shifted from a whitemilky colloidal solution to a deep red/black precipitate upon oxidativecross-linking as shown in FIG. 6B upon oxidation of the polymer withammonium persulfate. FIG. 6C shows an absorption spectrum for theoxidized cross-linked indole capped 1,3,5 benzene azadiene polymer.Absorption spectrum was determined by dissolving the soluble portion ofthe oxidized polymer in dimethylformamide and reading absorbance on aShimadzu UV/Vis mini 1240 from 180 nm to 1100 nm. Cyclic voltammeterywas performed to determine HOMO, LUMO and bandgap for the polymer (FIG.6D). The polymer was heat evaporated onto a glassy carbon electrode andcyclic voltammetry was performed using a Bio-Logics SP150 potentiostat,galvanostat in anhydrous acetonitrile TBAP purged with argon.

Example 6

Multifunctional organic substrates were synthesized as set forth inTable 3.

TABLE 3 Dimer cross-linking substrates. Reactant 1 Reactant 2 SolventProduct Indole-2-carboxaldehyde Hydrazine Ethanol Indole-2-azadieneIndole-5-carboxaldehyde Hydrazine Ethanol Indole-5-azadienePyrrole-2-carboxaldehyde Hydrazine Ethanol Pyrrole-2-azadieneThianaphthene-2- Hydrazine Ethanol Thianaphthene- carboxaldehyde2-azadieneFIG. 7 shows (from top to bottom) the synthesis of the 2-indoleazadiene, thianaphthene-2-azadiene, 5-indole azadiene, and 2-pyrroleazadiene.

The foregoing is illustrative of the present invention, and is not to beconstrued as limiting thereof. The invention is defined by the followingclaims, with equivalents of the claims to be included therein. Allpublications, patent applications, patents, patent publications, andother references cited herein are incorporated by reference in theirentireties for the teachings relevant to the sentence and/or paragraphin which the reference is presented.

That which is claimed is:
 1. A polymer prepared by polymerizing amultifunctional organic substrate with an oxidase or an oxidizing agentto form said polymer, said multifunctional organic substrate having astructure selected from the group consisting of:


2. The polymer of claim 1, wherein said multifunctional organicsubstrate has the following structure:

and said multifunctional organic substrate is reacted with serotonin andammonium persulfate to form said polymer.
 3. An electrochemical devicecomprising: a working electrode; a counter electrode; and said polymerof claim 1, wherein said working electrode is in operative communicationwith said counter electrode, and said polymer is in operativecommunication with said working electrode or said counter electrode.